Metal compounds of azo-dyestuffs and process of making same



Patented May 10, 1932 name was FRITZ $TRA'U'B AND \N'ALTIIg'lli-Qv ANDEIRAU, 0F BASEL, SWITZERLAND, ASSIGNORS 'TO THE emanation-F1013 FIRM SOCIETY OF CHEMICAL INIDlLTSTTttY IN BASLE OF BASEL, SWITZERLAND METAL coMroun'ns on nzo-nynsrurrsnnn rnoonss or MAKING SAME No Drawing. Application filed April 25, 1929, 'Serial No. 358,157 and in France, Japan, and Belgium,

March 8, 1929.

The present inventionrelates'to new and valuable metal compounds of aZo-dyestufis deriving from metals of: atomic weights ranging from 52 to 58.7. These metal compounds may contain either one metal alone or several metals. In the latter case one or several metals may also not belong to the above mentioned range of atomic weights. The dyestuiis according to the present invention are made by treating the poly-azm dyestufl of the general formula in which R is. an aryl residue which contains an OH-group in ortho-position to the -N=N group, and in which one of the I 'ws and one of the ys stand for an OH-group and the other w and the other 3/ for a hydrogen atom, one of the ms and one of the zs represent an SO H-group and the other a: and the other a a hydrogen atom, the sulfogroups being in meta-position to the OH- groups, further in which the two azo-groups are linked in ortho-position to the OH- groups and in which only one OH-group stands in 8-position, with agents yielding metals of atomic weights ranging-from 52' to 58.7 these agents being chosen in such a way that either one or several metals enterthe dyestuif molecule whereby in the latter case other metals may also enter the dyestuff molecule. The treatment may be applied in the course of the production of the said polyazo-dyestuff or to the finished dyestuff, either on the fiber, in the dye-bath or in substance. The dyestufis of the above formula may be made by coupling a diazo-compound which contains an OHsgroup i n ortho-position to v the N-=N group with a monoazo-dyestufi which is obtained by coupling a diazotized amino-naphtholofthe general formula in which the one an represents one OH-group and the other w a hydrogen atom, the one x an'sO H-group and the other 00 a hydrogen atom, and'in which the sulfo-group stands r in which the two ys and thetwo zs have the same meaning as above indicated, these two amin0-naphtho1s being chosen in such-a manner that the resulting aZo-dyestufis, contain only in one 8-position one OI-l-group.

The metal compounds of the azo-dyestufls of the above explained general formulaicleriving from metals of atomic weights ranging from 52 to 58.7 and, which may contain,

still other metals are when dry dark colored powders soluble in water and dilute alkalies to blue to dull reddish-blue solutions and in concentrated sulfuric. acid to blueto blackish-green, solutions, and dyeing vegetalolev fiberand especially artificial silk troi-n so-called regenerated cellulose grey,=greengrey to blue-grey tints. Particularlyuseful are those combinations which derive from; the

mono-azo-dyestufl" produced by coupling one molecular proportion of diazotized 2-amino -hydroxynaphthalene-7-sulfonic acid with a second molecular proportion of the same aminonaphthol-sulfonic acid in a feebly acid 5 medium. These'dyestuifs, however, do not dye the artificial silks from cellulose esters or cellulose ethers.

The following'examples illustrate the invention, the parts being by weight 1O Eazample 1.23.9 parts of diazotized 2- amino-5-naphthol-7-sulfonic acid are combined in presence of acetic acid with 28.9 parts of 2-amino-5-naphthol-7-sulfonic acid. After the coupling is complete the whole is rendered alkaline with parts of sodium carbonateand coupled with a solution of the diazonium compound from 14.3 parts of 4- chloro-2-amino-1-phenol. After some time the disazo-dyestulf of the formula Ho.s N=N NH;

, V V HOaS- V i V I V v 7 6-sulfonic acid. is then isolated.

, 54 parts of this dyestulf are dissolved in is then dissolved in 3000 parts of water and boiled for 24 hours with'a solution of chromium fluoride corresponding with 15 parts of Cr O The chromium compound is 'separated from its solution by means of common salt. It is a dark powder which dissolves in water, dilute alkalies, and concentrated sulfuric acid to a blue solution, dyeing the vegetable fiber as well as artificial silk sonar 7 has been formed and is separated. The prod uct is dissolved in 3000 parts of water, and the whole is heated during 25-3O hours in a reflux apparatus together with a solution of chromium fluoride corresponding with V 15 parts of Cr O Then the chromium compound is separated with common salt. When dry it forms a blackish powder which dissolves in water and dilute alkalies to a dull reddish-blue solution, and in concentrated sulfuric acid to a green-black solution. From a bath containing Glaubers salt and neutral or alkaline with sodium carbonate, vegetable fibers and artificial silk are dyed level grey tints. If in this example the equivalent quantity of 4-chloro-2-amino-l-phenol-G-sulfonic acid is employed as second diazotizing component in place of the 4-chloroaminophenol a dyestuif is obtained which dyes the said fibers blue-grey tints, whereas, when using 4-nitro chroming that dyes a green-grey of similar properties.

Ewample 2.23.9 parts of 'diazotized 2- amino-5-naphthol-7-sulfonio acid are combined by. known methods in an acetic acid solution with 24 parts of 2-an1ii1o-8-naphthol- 2-amino-1-phenol, a dyestuff is formed after in a neutral or alkaline Glaubers salt bath level grey-blue tints.

By using 4-chloro-2-aminophenol in the place of 5-nitro-2-aminophenol a chromium wherein one of the ws and one of the ys standing for an OH-group and the other to and the other y for a hydrogen atom, one of the ws and one of the zs representing an The dyestuff thus formed S'O H-group, and the other a: and the other 2 a hydrogen atom, the sulfogroups being in 'meta-pgsition to the OH-groups, and only one 0 -group standing in 8-position, with agents yielding metals of atomic weights ranging from 52 to 58.7.

2. A manufacture of new metal compounds of azo-dyestufi's. by treating a disazodyestufi' obtained by coupling in an alkaline medium one molecular proportion of a diazocompound of the benzene series containing a hydroXy-group in ortho-position to the =N group with a mono-azo-dyestuff of the general formula wherein one of the tos and one of the ys standing for an OH-group and the other w and the other 3 for a hydrogen atom, one of the ws and one of the zs representing an SO H-group, and the other no and the other 2 a hydrogen atom, the sulfo-groups being in SOaH with agents yielding metals of atomic weights ranging from 52 to 58.7.

4:. A manufacture of new metal compounds of azo-dyestuffs by treating a disazodyestufi' obtained by coupling in an alkaline medium one molecular proportion of a diazocompound of the benzene series containing a hydroXy-group in ortho-position to the +N=N group with "a mono-azo-dyestufi of the general formula a a on with agents yielding chromium.

5. As new productsfof. manufacture the metal compounds deriving from the metals of atomic Wei 'hts ranging from 52 to 58.7 of

obtained by coupling in an alkaline medium one molecular proportion of. a diazo-compound of the benzene series containing a hydroxy group in ortlio-position to the of the general formula wherein one of the We and one" of the ys standing for an OH-group and the-otherw and the other g for a hydrogen ,atom, oneof the ms and one of the .2s representing an sO H-group, and the other 02 and the other 2; ahydrogen atom, the sulfo-groups being in meta-posltion to the OiH-groupaandonly one 'OH-group standing in l8-posi tion, which products are whendry clark colored powders, soluble in water and dilute :alkalies toblue to reddish-blue solutions and inconoentrated sulfuric acidto greenish-blue to blue solutions, and dyeing vegetable fiber'andespecially artificial silk from so-called regenerated cellulosefast blue-grey to green-grey and :grey tints. V Y

6. As new products of manufacture the metal compounds of disazo-dyestufls which disazo-dyestufis are obtained by coupling v in "an alkaline medium one molecular proportion of a diazo-compound of the benzene series containing a hydroxy group in orthoposition tothe -N= N group with a monoazo-d-yes'tuff ofthe general formula ion wherein one of the 'ws and one of the ys standing for an OH-group and the other 'w and the other 3 for a hydrogen atom, one of the ms and one of thezs representing an so H-group, and the other 00 and the other e a hydrogen atom, the sulfo-groups being in meta-position to the OH-groups, and only one OH-group standing in 8-position, containing besides metals of atomic weights ranging from 52 to 58.7 still other metals capable of forming complex metal compounds with the aZo-dyestuffs, which products are when dry dark colored powders, soluble in water'and dilute alkalies to blue to reddish-blue solutions and in concentrated sulfuric acid to greenishcalled regenerated cellulose fast blue-grey to green-grey and grey tints.

7 .As new products of manufacture "the n metal compounds of disazo-dyestufl's which disazo-dyestuffs are obtained by coupling in analkaline medium one molecular proportion of a diazo-compound of the benzene series containing a hydroXy group in orthokalies to dull reddish-blue solutions, inconcentrated sulfuric acid to a green-black solution, and dyeingivegetable fiber and especially artificial silk from so-called' regenerated FRITZ STRAUB. WALTER ANDERAU.

position'to the ,N=N-- group with a monoazo-dyestufi of the formula SOaH scan which products form when drya dark colored powder, soluble in water and dilute al 

